JPH062809B2 - Curable resin composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a photocurable resin composition, and more specifically,
The present invention relates to a photocurable resin composition having good photocurability and a cured product having excellent electrical characteristics, heat resistance, and adhesiveness.

[Technical background of the invention and its problems] In recent years, in the fields of electric and electronic devices, with the increase in density and integration of wiring circuits, electrical insulating materials, paints, resist materials used in such fields have been developed. Has excellent electrical characteristics, especially at high temperatures,
It has been strongly desired that the adhesiveness to the adherend and the heat resistance of the coating film on the material surface are good.

Conventionally, as a result of various researches and developments in order to obtain a resin composition having good characteristics in response to such a request, as such a resin composition, an epoxy resin, an epoxy group in the epoxy resin Partial equivalent acrylated and / or methacrylic acid (hereinafter abbreviated as (meth) acrylic acid) epoxy resin obtained by addition reaction of acrylic acid and / or methacrylic acid (hereinafter abbreviated as (meth) acrylic acid) in an equivalent amount or less It is known to consist of Here, the partially (meth) acrylated epoxy resin is photocurable by an acryloyl group and / or a methacryloyl group (hereinafter, abbreviated as (meth) acryloyl group), and electrical characteristics and heat resistance imparted by curing the epoxy group. The resin has great utility as a resin having both properties such as adhesiveness and the like. Further, since this partial (meth) acrylated epoxy resin has a (meth) acryloyl group and an epoxy group in one molecule, a resin composition obtained by mixing an acrylate resin and / or a methacrylate resin and an epoxy resin. Had different properties and had more excellent photocurability. This part (meth) acrylic resin itself had good properties as described above, but in order to make the addition reaction proceed smoothly during the resin production, the fourth (meth) acrylic resin was used as a catalyst.
The catalyst remaining in the partially (meth) acrylated epoxy resin produced due to the progress of the reaction using an ammonium salt, a tertiary amine or the like significantly deteriorates the storage stability of the resin or the electrical properties of the cured product. It was the cause. Also, removal of residual catalyst is extremely difficult,
Often requires complicated washing or separation steps,
It was not industrially advantageous either. Therefore, there is a drawback that a small amount of the catalyst often remains even after the operation of removing the catalyst, so that sufficient electrical characteristics are not always obtained. Further, as a method of curing the partially (meth) acrylated epoxy resin, a method of using a photopolymerization initiator, a sensitizer or a thermal polymerization initiator alone or in combination for the polymerization of a (meth) acryloyl group is used. Method: For curing the epoxy group, a method of using a curing agent or curing catalyst such as an amine compound, an acid anhydride compound, a Lewis acid compound is generally used. However, when the conventional resin composition is used as an insulating material for electronic / electrical device parts, a sealing resin material or a resist material,
It has a drawback that it does not necessarily have sufficient electric characteristics or good workability.

[Object of the Invention] The object of the present invention is to eliminate the above-mentioned drawbacks, and a curable resin composition having good photocurability and having a cured product having excellent electrical characteristics, heat resistance and adhesiveness. Is to provide.

[Summary of the Invention] The resin composition of the present invention comprises: a) partial acrylate and / or acrylate obtained by reacting an epoxy resin with acrylic acid and / or methacrylic acid in the presence of an organometallic compound or an organophosphorus compound. Methacrylated epoxy resin; b) A sensitizer that initiates polymerization of acryloyl groups and / or methacryloyl groups by irradiation with light; and c) A curing catalyst containing an organoaluminum compound and an organosilicon compound. .

As the partially (meth) acrylated epoxy resin (a) used in the present invention, among those generally known as partially (meth) acrylated epoxy resin, particularly in the presence of an organometallic compound or an organophosphorus compound, Examples thereof include those obtained by reacting an epoxy resin with (meth) acrylic acid.

Further, in the present invention, such a reaction is carried out using an epoxy resin and (meth) acrylic acid in an amount equal to or less than the epoxy group in the epoxy resin. The equivalent ratio (latter / former) is preferably 0.1 to 0.9, more preferably 0.3 to 0.8. Here, when the equivalent ratio is less than 0.1, the photocurability of the obtained partial (meth) acrylated epoxy resin is poor, and when it exceeds 0.9, the cured product of the obtained resin is Poor in terms of adhesiveness, electrical characteristics, heat resistance, etc. As the component (a), a resin obtained by reacting an epoxy resin with (meth) acrylic acid in the presence of an organic metal compound or an organic phosphorus compound is used as described above. This is because the cured product of the curable resin composition of the present invention using the resin thus obtained has excellent electrical characteristics.

The epoxy resin used for producing the partially (meth) acrylated epoxy resin is not particularly limited as long as it is generally known as an epoxy resin, and specific examples thereof include bisphenol A type epoxy resin and bisphenol F. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin obtained by reaction of phenols or alcohols with epichlorohydrin, aromatic or aliphatic carboxylic acid And a glycidyl ester type epoxy resin obtained by the reaction of epichlorohydrin with. Further, as the organometallic compound, β-diketone, β-ketoester, salicylaldehyde derivative or the like as a ligand Al, Ga, Sn, Zr, Zn, Cu, Fe, Co, N
Examples thereof include complexes of i, Mn, Cr, V, Pt, Mo and Pd. Specific examples of the ligand include acetylacetone, benzoylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, CH ₃ COCH (CH ₃ ) COCH ₃ , (CH ₃ ) ₂ CHCOCH ₂ COCH (CH ₃ ) ₂ , CH ₃ COC
_{H 2 COOC 2 H 5, CH} 3 COCH 2 COOC 3 H 7, CH 3 COCH 2 COOCH 3, salicylaldehyde, 2-acetyl phenol, 2-hydroxy benzophenone. Specific examples of this complex include trisacetylacetonatoaluminum, tris (trifluoroacetylacetonato) aluminum, trisbenzoylacetonatoaluminum, trisethylacetoacetatoaluminum, trissalicylaldehydatoaluminum, tris (2-acetylphenolatoto). ) Aluminum, gallium (III) acetylacetonate,
Tin (II) acetylacetonate, Zirconium (IV)
Acetylacetonate, zinc (II) acetylacetonate, copper (II) acetylacetonate, iron (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) acetylacetonate, manganese (III) acetylacetonate , Chromium (III) acetylacetonate, vanadium oxide acetylacetonate,
Platinum (II) acetylacetonate, molybdenum acetylacetonate, and palladium (II) acetylacetonate are mentioned. Among them, the case of using an aluminum complex is preferable because it brings excellent effects particularly in electrical characteristics. Furthermore, Lewis bases such as tertiary phosphine and phosphite are effective as the organic phosphorus compound,
Of these, a third phosphine that acts as a weak Lewis base is preferable, and examples thereof include triphenylphosphine and
Tri- (p-tolyl) phosphine, tri- (p-methoxyphenyl) phosphine, tricyclohexylphosphine, 1,2-
Examples thereof include bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane.

Here, the amount of the organometallic compound used is usually 5% by weight or less, preferably 2% by weight or less, based on the epoxy resin. This is because when the amount used exceeds 5% by weight, the catalyst remaining in the resulting partially (meth) acrylated epoxy resin deteriorates the electrical characteristics of the composition of the present invention.
The amount of the organic phosphorus compound used is usually 0.5% by weight or less, preferably 0.05% by weight or less, based on the epoxy resin. When the amount used exceeds 0.5% by weight, the catalyst remaining in the resulting partially (meth) acrylated epoxy resin reduces the electrical properties and thermosetting properties of the composition of the present invention, and causes coloring. Because it will be.

The sensitizer (b) used in the curable resin composition of the present invention is
Any of sensitizers for initiating polymerization of a (meth) acryloyl group by light irradiation and used for general photopolymerization may be used, for example, biacetyl, acetophenone, benzophenone, benzyl, Examples thereof include benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, benzoyl peroxide, 1-hydroxycyclohexyl phenyl ketone, (1-hydroxy-1-methylethyl) phenyl ketone, and p-isopropyl-α-hydroxyisobutylphenone.

The amount of component (b) used is usually 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the partially (meth) acrylated epoxy resin. When the amount used is less than 0.5% by weight, the photocurability of the composition of the present invention is inferior, and when it exceeds 10% by weight, the electrical properties and solvent resistance of the cured product are inferior.

Curing catalyst used in the curable resin composition of the present invention (c),
Used to cure epoxy groups in partially (meth) acrylated epoxy resins. First, as the organoaluminum compound, an aluminum atom having an alkoxy group, an aryloxy group, an acyloxy group, a β-diketonato group,
A compound having a β-ketoesterato group bonded thereto is effective, and among these, a compound having a β-diketonato group and / or a β-ketoesterato group bonded thereto is preferable. Specific examples of such organoaluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, tris-p-methylphenoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum. ,
Tris stearate aluminum, tris butyrato aluminum, tris propionato aluminum, tris isopropionato aluminum, tris acetylacetonato aluminum, tris trifluoroacetyl acetonato aluminum, tris hexafluoroacetyl acetonato aluminum, tris ethyl acetoacetato aluminum, tris Examples include salicyl aldehyde aluminum, tris diethyl malonato aluminum, tris propyl acetoaceto aluminum, tris butyl aceto acet aluminum, tris benzoyl acetonato aluminum, tris-o-acetylphenolato aluminum, tris-o-propionylphenolato aluminum. These are used in one kind or in a mixed system of two or more kinds. The amount used is usually 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the component (a). When the amount used is less than 0.1% by weight, sufficient curing properties cannot be obtained, and when it exceeds 5% by weight, the electrical properties and adhesion are deteriorated. Next, as the organosilicon compound, a compound that produces a silanol group by heating and / or light irradiation is effective, and as an example, an alkoxysilyl group, an aryloxysilyl group, a peroxysilyl group and / or an α-ketosilyl group is included. Compounds. The organosilicon compound having an alkoxysilyl group and / or an aryloxy group is used together with the above-mentioned organoaluminum compound to develop the curing ability of the epoxy group by heating. Further, the organosilicon compound having a peroxysilyl group and / or α-ketosilyl group is used together with the above-mentioned organoaluminum compound to exhibit the curing ability of the epoxy group by light irradiation and / or heating. Of these organosilicon compounds, specific examples of the organosilicon compound having an alkoxysilyl group and / or an aryloxysilyl group include triphenylmethoxysilane, triphenylethoxysilane, triphenylpropoxysilane, triphenylbenzyloxysilane, Triphenylphenoxysilane, diphenyltolylmethoxysilane, diphenyltolylethoxysilane, diphenyldimethoxysilane,
Examples thereof include diphenyldiethoxysilane, diphenyldipropoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldiphenoxysilane. Specific examples of the compound having a peroxysilyl group and / or α-ketosilyl group include tert-butylperoxytriphenylsilane, di- (tert-butylperoxy) diphenylsilane, 1,1-dimethylpropylperoxytriphenylsilane and di- (1,1-dimethylpropylperoxy) diphenylsilane, 1-methylethylperoxytriphenylsilane, di (1-methylethylperoxy) diphenylsilane, tert-butylperoxymethyldiphenylsilane, tert-butylperoxydimethylphenylsilane . Specific examples of those having an α-ketosilyl group include benzoyltriphenylsilane, benzoylmethyldiphenylsilane, benzoyldimethylphenylsilane, acetyltriphenylsilane,
Examples include propionyltriphenylsilane, acetylmethyldiphenylsilane, benzoyltrimethylsilane, and benzoylmethoxydiphenylsilane. These are 1
It is used in one kind or a mixed system of two or more kinds. The amount used is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the component (a). When the amount used is less than 0.1% by weight, sufficient curing characteristics cannot be obtained, and when it exceeds 10% by weight, problems such as high cost and reduced adhesiveness may occur.

The curable resin composition of the present invention may be mixed with a solvent, a polymer compound, an antioxidant, a flexibility imparting agent, a dye, a pigment, a leveling agent, an antifoaming agent, an inorganic filler, etc., if necessary. Is also possible. The blending amount thereof is 300% by weight or less, preferably 200% by weight or less, based on the weight of the curable resin composition. If the amount of these compounds exceeds 300% by weight, the photocurability and / or thermosetting property of the curable resin composition will be poor, such being undesirable.

The curable resin composition of the present invention is easily manufactured by mixing and stirring the predetermined amounts of the above-mentioned components in a conventional manner.

The curable resin composition of the present invention is cured by light irradiation and heating, and exhibits excellent properties, that is, electrical properties, adhesiveness, mechanical toughness, and heat resistance. The wavelength of light advantageous for curing the curable resin composition of the present invention is usually 180 ~ 700
nm range, preferably 180-400 nm range. Also,
When the curable resin composition of the present invention is heat-cured, it is usually carried out in the range of 50 to 220 ° C, preferably 100 to 200 ° C. The curing method and order are not particularly limited, but usually, a method of heating after irradiation with light, a method of simultaneously performing irradiation with light and the like are used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, all "parts" are "parts by weight".

[Examples of the Invention] Example 1 Epoxy resin, Epicoat 828 (trade name, manufactured by Shell Co.,
Epoxy equivalent 190) 500 parts and acrylic acid 142 parts, using trisacetylacetonatoaluminum 13 parts as a catalyst and p-methoxyphenol 2.6 parts as a thermal polymerization inhibitor, at 110 ° C.
100 parts of partially acrylated epoxy resin (epoxy equivalent: 810, free acid: 0.15 meq / g, epoxy group / acryloyl group: 1/3) obtained by reacting for 12 hours, 30 parts of 1,4-dioxane,
(1-hydroxy-1-methylethyl) phenyl ketone 4 parts,
1 part of tris (ethylacetoacetato) aluminum and
A curable resin composition was prepared by mixing 3 parts of tert-butylperoxytriphenylsilane. This curable resin composition is uniformly applied on a copper plate using a bar coater, and the temperature is maintained at 80 ° C for 10
It was dried for a minute to remove the solvent and form a coating film having a thickness of 50 μm and having an adhesive property. This copper plate was introduced into a light irradiation device equipped with a 2kW high-pressure mercury lamp, and the average illuminance was 90mW / cm.
Illuminate at ² (at 365 nm) for 1 second. The coating hardened and became non-tacky. After that, heat curing was performed at 150 ° C. for 1 hour. The cured coating film was tough and showed good adhesiveness (cross-cut tape peeling test: 100/100). The electrical characteristics of the coating film are volume resistivity: 2 × 10 ¹⁶ Ω · cm (25 ° C), 5 × 10 ¹² Ω
・ Cm (160 ℃); Dielectric constant (50Hz): 4.1 (25 ℃), 5.1 (1
Dielectric loss tangent: 0.5% (25 ° C), 1.6% (160 ° C), showing excellent electrical insulation properties even at high temperatures.

Example 2 500 parts of epoxy resin Epicoat 828 and 170 of methacrylic acid
Parts were reacted at 115 ° C. for 12 hours in the presence of 10 parts of trisacetylacetonatoaluminum, 4 parts of cobalt (III) acetylacetonate and 2.7 parts of p-methoxyphenol. Dilute with 500 parts of toluene, wash with 3000 parts of water to remove residual methacrylic acid, separate the organic layer, and distill off the toluene under reduced pressure to remove partially methacrylic epoxy resin (nonvolatile content: 97% , Epoxy equivalent: 490, Free acid: 0.07meq / g, Epoxy group / methacryloyl group: 1/1)
Got 100 parts of this partially methacrylated epoxy resin, (1
-Hydroxy-1-methylethyl) phenyl ketone 4 parts, tris (ethylacetoacetato) aluminum 1 part, tert
-Butylperoxytriphenylsilane 2 parts, diphenyldiethoxysilane 2 parts and 1,4-dioxane 30 parts were blended to obtain a curable resin composition. This curable resin composition was applied in the same manner as in Example 1 and then irradiated with light for 2 seconds,
Subsequently, heat curing was performed at 150 ° C. for 30 minutes and 200 ° C. for 30 minutes.
The cured coating film had excellent electrical properties even at high temperatures. Volume resistivity: 3 × 10 ¹⁶ Ω ・ cm (25 ℃), 4 ×
10 ¹³ Ω ・ cm (200 ℃); Dielectric constant (50Hz): 3.7 (25 ℃),
4.3 (200 ℃); Dielectric loss tangent: 0.5% (25 ℃), 2.5% (200
℃).

Comparative Example Epoxy resin Epicoat 828 (500 parts) and acrylic acid (142 parts) were reacted at 110 ° C. for 5 hours in the presence of choline chloride (3 parts) and p-methoxyphenol (2.6 parts). After diluting with 500 parts of toluene and washing with 3000 parts of water, the organic layer is separated, and the toluene is distilled off under reduced pressure to partially acrylate epoxy resin (nonvolatile content: 95%, epoxy equivalent: 970, free acid: 0.00m
eq / g, epoxy group / acryloyl group: 1/3) was obtained. 100 parts of this partially acrylated epoxy resin, (1-hydroxy-
1-methylethyl) phenyl ketone 4 parts, hexahydrophthalic anhydride 15 parts, dimethylbenzylamine 1 part and 1,4-
30 parts of dioxane was blended to obtain a curable resin composition. This curable resin composition was cured under the same conditions as in Example 1. The electrical properties of the cured product deteriorated significantly above 100 ° C. Volume resistivity: 3 × 10 ¹⁵ Ω · cm (25 ℃), 1.2 × 10
¹² Ω ・ cm (100 ℃); Dielectric constant (50Hz): 4.3 (25 ℃), 6.
3 (100 ℃); Dielectric loss tangent (50Hz): 1.7% (25 ℃), 9.6%
(100 ° C).

Example 3 Epoxy resin, Epicoat 828 150 parts and epoxy resin Epicoat 1001 (trade name, manufactured by Shell Co., epoxy equivalent 48
0) 350 parts of acrylic acid and 82 parts of acrylic acid are reacted in the presence of 14 parts of trisacetylacetonatoaluminum and 2.5 parts of p-methoxyphenol for 12 hours at 110 ° C. to obtain a partially acrylated epoxy resin (epoxy equivalent: 1550 , Free acid: 0.00me
q / g, epoxy group / acryloyl group: 1/3, melting point: 50-60
C.) 100 parts, benzyl dimethyl ketal 2 parts, benzophenone 2 parts, tris (ethylacetoacetato) aluminum 1 part, diphenyldiethoxysilane 3 parts and 1,4-dioxane 50 parts to form a curable resin composition. did. This curable resin composition was applied onto a copper clad laminate and dried at 80 ° C. for 10 minutes to remove the solvent, to give a non-adhesive 40 μm thick coating film. A negative mask was brought into close contact with this coating film, and light irradiation was carried out for 3 seconds in the same manner as in Example 1. Remove the negative mask, 1,
When the coating film was developed using a mixed solvent (95: 5) of 1,1-trichloroethane and ethyl cellosolve, an image-like coating film corresponding to a negative mask was obtained. Following this, 150
When heat-cured at 1 ° C. for 1 hour, the adhesiveness, electrical characteristics, solder heat resistance, etc. were excellent. Cross-cut tape peeling test: 100/100, electrical characteristics, volume resistivity: 3 × 10 ¹⁶ Ω
-Cm (25 ° C); dielectric constant (50Hz): 4.1 (25 ° C); dielectric loss tangent (50Hz): 0.5% (25 ° C). In addition, no change was observed in the appearance, adhesiveness, etc. of the coating film after immersion in a solder bath at 260 ° C for 1 minute.

Example 4 500 parts of epoxy resin Epicoat 1001 and 53 parts of methacrylic acid are dissolved in 300 parts of 1,4-dioxane and reacted at 120 ° C. for 6 hours in the presence of 0.1 part of triphenylphosphine and 2.5 parts of p-methoxyphenol. Partially acrylated epoxy resin (nonvolatile content: 67%, epoxy equivalent: 1790,
Free acid: 0.00 meq / g) 150 parts, benzyl dimethyl ketal 4 parts, trissalicyl aldehyde aluminum 1 part and diphenyldiethoxysilane 4 parts were blended to obtain a curable resin composition. Light irradiation and development were carried out in the same manner as in Example 3 to obtain an image-like coating film suitable for a negative mask. Then, by heat-curing at 150 ° C. for 1 hour, a coating film having excellent adhesiveness, electrical characteristics, bander heat resistance, etc. was obtained.

[Effects of the Invention] As described in detail above, the curable resin composition of the present invention has good photocurability, and the obtained cured product has excellent electrical characteristics, adhesiveness, and heat resistance. Because there is
Applications such as electrical insulating materials, paints, and resist materials can be expected, and their industrial value is extremely large.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Moriha Wada 1 Komukai Toshiba-cho, Kouki-ku, Kawasaki-shi, Kanagawa Inside Toshiba Research Institute, Inc. (56) Reference JP-A-61-159461 (JP, A)

Claims (7)

[Claims] 1. A) partially acrylated and / or methacrylic epoxy resin obtained by reacting an epoxy resin with acrylic acid and / or methacrylic acid in the presence of an organometallic compound or an organophosphorus compound; b) light A curable resin composition comprising a sensitizer that initiates polymerization of an acryloyl group and / or a methacryloyl group upon irradiation; and c) a curing catalyst containing an organoaluminum compound and an organosilicon compound. 2. A partially acrylated and / or methacrylated epoxy resin is a resin obtained by reacting acrylic acid and / or methacrylic acid with an epoxy resin at an equivalent ratio of 0.1 to 0.9. The composition according to claim 1 in the range. 3. The organometallic compound is aluminum (A
l), gallium (Ga), tin (Sn), zirconium (Zr), zinc (Zn), copper (Cu), iron (Fe), nickel (Ni), cobalt (Co), manganese (M
n), chromium (Cr), vanadium (V), platinum (P
The composition according to claim 1, which is a compound consisting of at least one metal selected from the group consisting of t), molybdenum (Mo) and palladium (Pd). 4. The composition according to claim 1, wherein the organic phosphorus compound is a tertiary phosphine. 5. The composition according to any one of claims 1 to 4, wherein the organosilicon compound is a compound having an alkoxysilyl group and / or an aryloxysilyl group. 6. The composition according to any one of claims 1 to 4, wherein the organosilicon compound is a compound which forms a silanol group upon irradiation with light. 7. The composition according to claim 6, wherein the compound which forms a silanol group upon irradiation with light is a compound having a peroxysilyl group and / or an α-ketosilyl group.